Mineral oil compositions



Patented Apr. 2 9, 1952 MINERAL OIL COMPOSITIONS Leonard E. Beare,Lansing, 111., assignor to Sinclair Refining Company, New York, N. Y., acorporation of Maine No. Drawing. Application February 17, 1949, SerialNo. 77,057

S'Claiins. (01. 252-463) .This'invention relates to novel lubricatingoil compositions. More particularly, it is concerned with'gear oils andwith, especially, universal gear lubricants.

A satisfactory universal gear lubricant'is capable of lubricatingautomotive and truck hypoids while performing, atthe same time, as areasonably satisfactory lubricant for the other gears and transmissionsfound in such vehicles. Accordingly, the problem is' to provide asingular gear lubricating composition which is satisfactory for theconditions encountered at high speed-low torque operations on one hand,and, conversely, at low speed-high torque operations on the other. Inaddition, these lubricants must be 'efi'ective without objectionablechanneling, rusting, corrosion, foaming, or additive separation invarious environments.

Theapplications Serial No. 761,994, filed July 18, 1947, now Patent No.2,515,222, by William S. Hoock and Milton P, Kleinholtz, and Serial No.762,003, filed July 18, 1947, by Robert L. May, describe and claim newcompositions of matter resulting from the reaction of a bieyclicterpene,

sulfur, and a phosphorus sulfide. I have now;

discovered that the compounds to which these applications are directedare especially effective in compounding highly satisfactory gearlubricating compositions when such products are used in conjunction withan organic chlorinecontaining compound.

The proportions of the addends used in the Generally, the range of theconcentration of the compounds described in the aforementionedapplications is most satisfactory from 4 to- 12% by weight on thecompounded lubricant. How ever, I prefer andrecoznmend anaddition ofabout 8%.

The rangeof concentrations of the chlorinecontaining compounds is mostsatisfactory from about 3 to 8%, and is dependent in great part upon thechlorinated hydrocarbon employed.

The exact mechanism of the reactions orming thesecompounds is unknown,nor has amo lecular weight or structure been assigned to them because oftheir complexity. When normally prepared, the additive is solid atordinary temperatures and when employed as a lubricating oil addend, itis best incorporated in the form of an oil solution having a-phosphoruscontent of, for example, about 1.5 to 4.0%, using asthe solvent oil apetroleum fraction whose viscosity and other characteristics are notsuch asto adversely affect the lubricating qualities of the compound.

Although these compounds may be prepared using any proportions of theidentified reactants, Where the product is to be used in the compoundingof a lubricant, as here, the most satisfactory proportions have beenfound to be about 3lto-5 moles of the bicyclic terpene and about0.5 to 5atoms of sulfur, for each mole of the phosphorus sulfide.

A terpene most advantageously used is alphapinene. However, in place ofalpha-pinene, a reactant comprising substantially alpha-pinene in.admixture with other related terpenes, such as camphenes and dipentenes,has been found to be satisfactory. A phorphorus sulfide productive ofhighly desirable addends within thescope of my invention is, forexample, phosphorus pentasulfide. A light petroleum fraction that may beused to prepare an oil concentrate containing these reaction productsisa Mid-Continent solvent-treated neutral.

The following examples are illustrative of, and indicate the procedureby which, these novel compositions of matter are. made.

EXAMPLE A In a five-liter, three-necked flask equipped with a mechanicalstirrer anda thermometer were placed 1088 grams (8 moles) ofalphapinene. An electric heating mantlewas used to heat the alpha pineneto 275 F. Theheat was turned "oil and 444 gms. (2Jmo1es) of-powderedphosphorus pentasulfide were added portionwise while maintainingvigorous stirring. The initial portions weighed approximately 40 gms.and after about half of the phosphorus pentasulfide was added, theportions were increased to about gms. each. Meanwhile the temperature:was maintained between 270 and 280 F. as regulated by the .rate of thephosphorus pentasulfide additions. After 1% hours, all the phosphoruspentasulfide had'been added and the exothermic reaction was no longerapparent. The heater was then turned on'and the temperature wasmaintained at 275 to 280 F. for two hours. 96 gms. (3 atoms) of powderedsulfur were added in increments of 32 gms. each at 45-minute intervals.After the second addition of sulfur, the temperature was raised to 325to 340 F. and so maintained for 5% hours after all the sulfur had beenadded. The heater was turned off and the product was diluted with 2302gms. of a Mid- Continent neutral lubricating oil. The product wasfiltered at a temperature of 200 F. using a commercial filter aid. Uponanalysis it was found to contain 11.13% sulfur and 2.98% phosphorus. Theacid number was 3.8 and the saponification number 59.

EXAMPLE B In a five-liter, three-necked flask equipped with a mechanicalstirrer, a reflux condenser, and a thermometer were placed 1088 gms. (8moles) of alpha-pinene. An electric heating mantle was used to heat thealpha-pinene to 275 F. The heat was turned off and 444 gms. (2 moles) ofpowdered phosphorus pentasulfide were added portionwise whilemaintaining vigorous stirring. The initial portions Weighedapproximately 40 gms. and after about half of the phosphoruspentasulfide was added, the portions were increased to about 80 gms.Meanwhile the temperature was held at 275 F. as regulated by the rate ofaddition of the phosphorus pentasulfide. After 1 /2 hours all of thephosphorus pentasulfide had been added and the exothermic reaction wasno longer evident. The heater was then turned on and the reactants weremaintained at 275 F. for 2 hours. 192 gms. (6 atoms) of powdered sulfurwere added in toto and the temperature was increased to 325 F. At thistime another exothermic reaction occurred and the temperature roserapidly to 366 F. The flask was cooled to 325, F. and maintained at thistemperature for 6 hours. The heat was turned oil and the product wasdiluted with 2206 gms. of a Mid-Continent neutral lubricating oil. Thefinal product was filtered at 200 F. using a commercial filter aid. Itcontained 12.85% sulfur and 3.08% phosphorus. The acid andsaponiflcation numbers were 16.4 and 100 respectively.

EXAMPLE C In a five-liter, three-necked flask equipped with a mechanicalstirrer, a reflux condenser, and a thermometer were placed 1088 gms. (8moles) of alpha-pinene. An electric heating mantle was used to heat thealpha-pinene to 275 F. The heat was turned off and 444 gms. (2 moles) ofpowdered phosphorus pentasulfide were added portionwise whilemaintaining vigorous stirring. The first portions weighed approximately40 gms. and after about half of the phosphorus pentasulfide was added,the portions were increased to about 80 gms. each. The addition ofphosphorus pentasulfide required approximately 2 hours and thetemperature was maintained at about 275 F. throughout this step. Thereactants were kept at this temperature for an additional 2 hours andthen 288 gms. (9 atoms) of powdered sulfur were added in three equalportions over a period of 45 minutes. After all the sulfur had beenadded, the temperature was raised to 325 F. The temperaturewasmaintained at about 325 F. for 6 hours after the final addition ofsulfur was made and then the heater was turned off and 2110 gms. of aMid-Continent neutral lubricating oil were added. The final product wasfiltered with a commercial filter aid at a temperature of 200 4 F. Ithad an acid number of 25.4, a saponification number of 109, andcontained 15.10% sulfur and 2.93% phosphorus.

EXAMPLE D In a five-liter, three-necked flask equipped with a stirrer, areflux condenser, and a thermometer, were placed 1360 gms. (10 moles) ofalphapinene. An electric heating mantle was used to heat the alphapinene to 275 F. The heater was turned off and 444 gms. (2 moles) ofpowdered phosphorus pentasulfide were added in increments of 40 to gms.each at such a rate as to maintain the temperature at about 275 F. Thereactants were stirred vigorously during the phosphorus pentasulfideaddition. The heater was then turned on and the alpha-pinene-phosphoruspentasulfide mixture was maintained at approximately 275 F. for anadditional 2 hours. 192 gms. (6 atoms) of sulfur were added in threeequal increments over a period of 45 minutes. After all the sulfur hadbeen added, the temperature was raised to 325 F. and an exothermicreaction momentarily raised the temperature to 377 F. The flask wascooled to 325 F. and so maintained for 6 hours. The product was dilutedwith 1934 gms. of a Mid-Continent neutral lubricating oil and, aftercooling to 200 F., was filtered with a commercial filter aid. It had anacid number of 5.4 and a saponification number of 133 and contained12.35% sulfur and 3.08% phosphorus.

EXAMPLE E In a five-liter, three-necked flask equipped with a stirrer, areflux condenser, and a thermometer, was placed 1360 gms. 10 moles) ofalpha-pinene. An electric heating mantle was used to heat thealpha-pinene to 275 F. The heater was turned off and 444 gms. (2 moles)of powdered phosphorus pentasulfide were added in increments of 40 to 80gms. each at such a rate as to maintain the temperature at about 275 F.The alphapinene was stirred vigorously during the 1% hours while thephosphorus pentasulfide was introduced. The heater was turned on and thereactants were maintained at 275 F. for an additional 2 hours. 288 gms.(9 atoms) of sulfur were added in three equal portions over a period of2 hours. The first portion of sulfur was added at a temperature of 275F. and the heater was turned up until a temperature of 317 F. wasreached. At this stage an exothermic reaction occurred and the heaterwas removed. The maximum temperature was 342 F. After addition of thebalance of sulfur at about 317 F., the reaction was continued at 325 F.for 6 hours and the heater was turned off. The product was diluted with1838 gms. of a Mid-Continent neutral lubricating oil and filtered at 200F. using a commercial filter aid. It analyzed 15.42% sulfur and 3.14%phosphorus. The acid number was 10.4 and the saponification number 109.

EXAMPLE F In a five-liter, three-necked flask equipped with a mechanicalstirrer, a reflux condenser, and a thermometer were placed 1088 gms. (8moles) of alpha-pinene. An electric heating mantle was used to heat thealpha-pinene to 275 F. The heater was turned off and 222 gms. (1 mole)of powdered phosphorus pentasulfide were added portionwise, withstirring, at such a rate as to maintain the temperature at 275 to 285 F.during the 50 minutes required for the phosphorus pentasulfida addition.Theheater was: turned a Mid-Continent neutral oil wereadded, and theproduct wasfiltered at 200 F. witha commercial filter aid; It analyzed15.93% sulfur and. 1.64% phosphorus. The-acid numberwas- 25.1.a-nd thesaponification number 108.

EXAMBLE: G

In. a fiveeliter, three-necked flask equipped with a stirrer, refluxcondenser, and a thermometer, were placed 1360 gms. moles) ofalphapinene. An electric heating mantle was'used to heat thealpha-pinene to 275 F. 10' gms. of powdered sulfur were added withstirring and thetemperature was raised to 300'F. 10 more gms. of sulfur.were added and the temperature was raised until the alpha-pinenerefluxed vigorously (310, to 316 F.). 172 gms. (to complete a total of 6atoms) of sulfur were added and the temperature was maintained at 310 to316 F. for 3 hours. The heater was turned off and the product was cooledto 275 F. 444 gms. (2 moles) of powdered phosphorus pentasulfide wereaddedportionwise. Approximately 40-gm. portions were added initially andafter about half of the phosphorus pentasulfide was added, the portionswere increased to about 80 gms. The temperature was controlled by therate of the phosphorus pentasulfideadditions so that'it did not exceed285 F.

After 1%, hours, all the phosphorus pentasulfide had been added and theexothermic reactionwas EXAMPLE H In a five-liter, three-necked flaskequipped with a stirrer, a reflux condenser, and a thermometer, wereplaced 1360 gms. (10 moles) of alpha pinene. An electric heating mantlewas used to heat the alpha-pinene to 305 F; 40 gms. of powdered sulfurwere'added, with stirring, and no evidence of an exothermic reaction wasnoticed. The solution was cooled to 285 F. and 248 gms. (to make a totalof 9 atoms) more sulfur were added. Heat was applied and the temperatureslowly rose to 305 F. After heat ing 2 hours at 305 F., the product wascooled to 275 F. and the heater turned ofi; 444 gms. (2 moles) ofpowdered phosphorus pentasulfide were added in increments of 40 to 80gms. each at such a rate as to maintain the temperature at 270m 290 F.The addition of phosphorus p'entasulfide-required 1 hours. The heaterwas" 384' gms. (12 atoms). of: sulfur were' 6'. turned on: and-the,temperature,- was. raised. to 300 F. and maintainedtfort.hours.The'heater. was turned oif and 1838 gms. of a Mid-Continent neutrallubricating oil were added. The final product, was, filtered at 200 F.using a com mercial filter aid. It had a phosphorus content of 3.24%, asulfur content of 15.49% and showed a saponification number of 98 and anacid numberof 35.4.

EXAMPLE I In a five-liter, three-necked flaskequipped with a stirrer, areflux condenser, and a thermometer, were placed 1360 gms. (10' moles)of alpha-pinene and 384 gms. (12 atoms) of.pow-- dered sulfur. Thestirrer wasstartediand the reactants were heated to 310 F.,by meansofjan. electric heatin mantle. After 1 hour, 9.6. gms. (3 atoms) additionalsulfur were, added and the: temperature was maintained at 310 F. for 21hours. The heater was turned off and the, reactants were cooled. to 275F. 278 gms. (1%. moles) of powdered phosphorus pentasulfide, were thenadded portionwise over a period of 1%. hours: The temperature was keptat 275 to 285 F. during the phosphorus pentasulfide addition by addingthe reactant in increments of 15 to 20- gms. each. The heater was turnedon and the temperature was held at 300 F. for 3 hours. The heater wasturned off, 2118 gms. of a Mid--- Continent neutral lubricating oil wereadded, and the product was filteredat200 F. with a commercial filteraid. It had a phosphorus content of 1.65%, a sulfur content of 16.17%and showed a saponification number of. 98 andan acid number of, 23.9,.

EXAMPLE J 1088 gins. (8 moles) of alpha-pinena were. charged into afive-liter, three-necked flaskv equipped with a mechanical stirrer andathermometer. The alpha-pinene was heated to 280 F. with an electricheating mantle, and 96 gins. of sulfur (3v atoms) were added. Thereaction mixture was stirred and heated at a refluxtemperature of 305 to315 F. for 3 hours. The electric heating mantle was then removed and 444gms. (2 moles) of phosphorus pentasulfide were added portionwise, whilemaintaining vigorous stirring, at a 'sufiicientrate to maintain thetemperature at 275 tov 290 F. for 1 hours. The reaction mixture washeated at 275 to 285F. for an additional 2 hoursand then raised to 300F.v for an, additional 3 hours. 2302 gms. of a Mid"- Continentsolvent-treated neutral oil were then blended with the reaction mass.This oil concentrate was. allowed to stand overnight. It wasthenheatedto F. and filtered with afilter aid. The product analyzed3.46% phosphorus and 10.56% sulfur and had an acid number of 2.70 and asaponification number of, 58.6.

Various chlorine containing hydrocarbons may. be used in preparing theseimprovedlnoveli lubrieating compositions; the intended use of thelubricant is determinative of'the nature and char.- acteristics of thesechlorinated'addends. Chlorinated naphthalenes and chlorinated paraffinwaxes are illustrative of highly desirable compounds of this nature. Inaddition, chlorinated diphenyls may be, used. In. each case, theimportant considerations are the effective, amounts. of chlorine thatare available and the solubility of the selected additive in oil.Generally, chlorinated naphthalenes and parafiin waxes having a minimumtendency to evolve free hydrogenchloride in storage or upon moderateheating are and tested.

compounds most advantageously employed in the preparation of thelubricants.

1 The chlorine content of the chlorinated naphthalenes and the paraffinwaxes will vary greatly and amounts ranging from about 50 to 70%chlorine in naphthalenes and about 35 to 75% chlorine in paraffin waxeshave been found to be satisfactory. However, the criteria fordetermining the eiiicacy of a chlorine-containing substance, asmentioned above, appear to be primarily dependent upon the effectiveamounts of chlorine available and the solubility of the compound in oil.

The range of concentration of these compounds in the improvedlubricating composition is most satisfactory from about 3 to 8% byweight on the compounded lubricant. In particular, 6% of a chlorinatedparafiin wax containing approximately 40% chlorine has been found to behighly satisfactory.

To further illustrate my invention, various lubricating compositionshave been compounded The standard Federal-specified methods forevaluating the performance of universal gear lubricants, which I haveused, are described in the Coordinating Research Council Handbook, 1946edition. In addition, certain other tests, namely, the Timken Weed-OutProcedures, were resorted to. Essentially, these latter tests areperformed as follows:

The Timken L- Weed-Out Procedure No. 1.--Timken L-20 Weed-Out Proceduresemploy the Timken testing machine of the Coordinating Research CouncilsTimken Machine Test (CRC L-18-545), with necessary modifications asrequired to operate under the following conditions:

Test cup speed 100 R. P. M.

Lever load 198 pounds Oil temperature 250 F.

Oil feed Rapid circulation over entire cup Duration 16 hours The totalweight loss of the test cup and block are determined and these parts areexamined for failure.

The Tz'mken L-20 Weed-Out Procedure N0. 2.-This test is identical toProcedure N0. 1 except that the test block is continuously moved backand forth beneath the test cup in a direction paralleling the lever arm,for a distance of 0.13 inch, four times per minute. In addition, thecoefiicient of friction and sludge formation, particularly of depositson the Timken Test Block, are recorded during the 16 hour wear test.

Additional one-hour tests are made at higher speeds. These testsindicate the maximum R. P. M., to the nearest R. P. M., at Which 198pounds can be carried for one hour without any evidence of failure byscoring, grooving, or smearing. Timken L-20 Procedure No. 2 is preferredover Procedure No. 1 because wear occurs under line contact conditionsat unit loads closely simulating those in hypoid ears under high torqueconditions. Uncompounded base oils will usually fail at from 25 to ofthe regular 198 pound lever load. Commercial hypoid gear lubricantswhich meet standard specifications give from 4 to 15 mgs. of wear and asmooth bright surface. Commercial hypoid gear lubricants which pass theCRC High Speed Axle Test but fail the CRC High Torque Axle Test givefrom to 300 mg. of wear and heavy grooving.

The following examples illustrate various universal gear lubricating oilcompositions, as well as the results of certain evaluating testsperformed upon each lubricant. The compositions contain identifiedaddends that were blended with a base oil, the characteristics of whichare indicated in Table I. The pour depressant compounded into thelubricating oil compositions was an octadecyl methacrylate polymer. Theantifoam agent was a silicone polymer, while the solubilizer was a 10%concentrate of calcium sulfonate in oil. This additive was included inseveral of the compositions primarily for its value as a solubilizer,although it has utility also as a rust and sludge inhibitor. However,the presence of this compound is not critical, since its functions arenot essential to the practice of my invention. In particular, lowpercentages of the sulfonate concentrate, for instance, 1%, do notappreciably affect load capacity. On the other hand, appreciableamounts, for instance 5% or more, will undoubtedly decrease loadcapacity, chemical activity, and oxidation sludging of the lubricant.

Composition XII shows that both a chlorinated naphthalene and achlorinated parafiin wax may be added together.

Preferred reaction products are the preparations of Examples A and D.Eight per cent of such preparations with 6% of either a chlorinatednaphthalene containing 57% chlorine or a chlorinated paraffin waxcontaining 40% chlorine are highly preferable addition compounds whenemployed in the recommended base oil. The results also indicate that thechlorinated paraflin wax of 40% chlorine content and the chlorinatednaphthalene of 57% chlorine content are approximate equivalents.However, the low cost and great solubility of the par-afiin wax favorits use.

Not all of the Coordinating Research Council Gear Lubricant EvaluationTests have been per-' formed upon each of the illustrative gear oilcompositions. However, a sufficient number of the more critical testswere made to show the most useful properties. In fact, essentialproperties of a satisfactory gear lubricant may be evaluated by the useof a singular test, namely, the Timken L-20 Weed-Out Procedure.

TABLE I Composition Mid-Continent solvent-treated neutral oil,

weight per cent 16.97 Mid-Continent solvent-treated bright stock oil,weight per cent 82.83 Pour depressant, weight per cent 0.20

Properties Flash point, F 460 Viscosity, S. U. S. at F' 1216 Viscosity,S. U. S. at 210 F 96 Viscosity index 91 Pour point, F 5 Sulfur, per cent0.28

Composition I The lubricating oil composition was composed of by weight:

Per cent Preparation of Example D 2 57% Clz-containing naphthalene 6solubilizer 1 Base Oil 91 Composition II .The lubricating oilcomposition was composed of by weight:

Per cent Preparation of Example E 2 57% Gi -containing naphthaleneun 6Solubilizer l Base oil 91 The Timken Procedure No. 1showed a 29 mg. lossafter 16 hours of wear, the surfaces being lightly grooved. Thelubricant failed this test.

The copper strip was a dark peacock color after.

1 hour at 250 F. There was no'rustformation in the Rust Protection Test.

Composition III The lubricating oil composition was composed of byweight:

i V I t Per cent Preparation of Example G 2 57 cl z-containingnaphthalene 6 Solubilizer 1 Base oil 91 The Timken' Procedure No; 1showed a145 mg. loss after16 hours of wear, the surfaces being heavilygrooved." The lubricant failed this test.

'The copper'strip after 1 hour at 250 F. was a light peacock color. TheRust Protection .Test showed no rust formation.

Composition IV The lubricating oil composition was composed of byweight:

1 Per cent Preparation of Example H '2 57% Gig-containing naphthalene 6Solubilizer '1 Base o i1 9 Y The Tir'nken Procedure No. 1 showed a 15mg. loss after 16 hours of wear, the surfaces being in good condition;the lubricant passed this test. The copper strip after 1 hour at 250 Fwas a light peacock color and the RustProtection' Test indicated that norust had formed.

Composition V n The lubricating oil composition was composed of byweight:

, Per cent Preparation of Example A ,4 57% Gig-containing naphthalene 6Solubilizer. 1

Basevoil 8.9

ThejTimk'en Procedure No. 1 revealed that there was a 6 mg. loss after16 hours of wear. and the surfaces showed a slight trace of grooving.The

lubricant was on the bo'rderline of passing this test' The'copper stripwas a light peacock color after 1 hour at 250 F., and there was no rustformation in the Rust Protection Test. The lubricant passed the HighSpeed Axle Test (CRC 15-19-6 15) and failed the High Torque Axle Test('CRC L- 2p-545) because of grooving. r V

0? Composition VI The lubricating oil composition was composed of byweight:

Per cent Preparation of Example D 4 57% Clz-containing naphthalene 6Solubilizer 1 Base oil 89 The Timken Procedure No. 1 showed a 6mg.

loss after 16- hours of wear, and the surfaces showed a trace ofgrooving. The lubricantreceived a borderline rating in this test. Thecolor of the copper strip after 1 hour at 250 F. was dark peacock. Norust formed in the Rust Protection Test.

- Composition VII The lubricating oil composition was composed of byweight:

Per cent Preparation of Example J 4 57% Ch-containingnaphthalene 1 6Solubilizer 1 Base oil 89 The Timken Procedure No. 1 indicated thatthere was a 3 mg; loss after1'6'hoursof wear,

and the surfaces were ingood condition As. a; result the lubricantpassed this test. The copper strip was a light peacock color after 1hourat 250 F. H The Rust Protection Test showed no rust formation.

Composition VIII A I The lubricating oil composition was composed of byweight:

' 7 Per cent Preparation of Example G 4 57% Clz-containing naphthalene 6Solubilizer ..V 1

"Base oil 89 The'TinikenProcedure No. 1 showed a 16 mg. loss after 16hours of wear, the surfaces being lightly grooved. Asa result, thelubricant failed this test. The copper strip was a light peacock colorafter 1 hour at 25051 There was no rust formation in the Rust ProtectionTest.

H Composition IX u The lubricating oilcomposition was composed of byweight: 1 v

Per cent Preparation of Example A 8 57% Clz-containing naphthalene 6Solubilizer 1 Base oil TheTimken Procedure No. 1 showed an 11 mg.

loss after 16 hoursofwear, andthe surfaces were.

in goodcondition. .As. a result the lubricant passed this test. Thevcolor .of. the. copper strip after -1 hourat 250 F. was light peacock..The

Rust Protection Test revealed that no rust formed.

" Compositi n X The lubricating oil composition was composedofby'weight: r a i V v Per cent Preparation of Example A; 8 57(Ila-containing 'naphthalene 6 Base oil 86 .The-Timken L-20 ProcedureNo. 2 revealed that.

there was 'a 13 mg. loss after 16 hours of W621, the surfaces being ingood condition. The safe R. P; M. were and the lubricant passed thistest.

There was no rust formation in the Rust Protection Test.

Composition XI The lubricating oil composition was composed of byweight:

Per cent Preparation of Example A 8 70% Clz-containing naphthalene 4Neutral oil 15.80 Bright stock oil 71.94 Pour depressant 0.26 Antifoamagent 0.0005

The Timken Procedure No. 2 revealed an 11 mg. loss after 16 hours ofwear, the condition of the surfaces being good. The safe R. P. M. were125 and the lubricant passed this test. The Rust Protection Test showedno rust formation, while the Storage Solubility Test (CRC 11-22-445) wasalso passed.

Composition X1 1 The lubricating oil composition was composed of byweight:

Per cent Preparation of Example A 8 70% Clz-containing naphthalene 4 40%Ola-containing paraffin wax 1.5 Base oil 86.5

The Timken L-20 Procedure No. 2 revealed a 7 mg. loss after 16 hours ofwear, the surfaces being in good condition. The safe R. P. M. were 225,and the lubricant passed this test.

Composition XIII The lubricating oil composition was composed of byweight:

Per cent Preparation of Example A 8 40% Clz-containing paraffin wax 4.5Neutral oil 22.70 Bright stock 64.54 Pour depressant 0.26 Antifoam agent0.0005

The Timken L-20 Procedure No. 2 showed a 14 mg. loss after 16 hours ofwear, the surfaces being in good condition. The safe R. P. M. were 200and the lubricant passed this test. The copper strip after 1 hour at 250F. was a dark peacock color, while the Rust Protection Test revealedthat no rust had formed.

Composition XIV The lubricating oil composition was composed of byweight:

Per cent Preparation of Example D 8 57% Clz-containing naphthalene 6Solubilizer 1 Base oil 85 The Timken Procedure No. 1 showed a 4 mg. lossafter 16 hours of wear, and the surfaces were in good condition. As aresult the lubricant passed this test. The color of the copper stripafter 1 hour at 250 F. was a dark peacock. No rust formed during theRust Protection Test.

Composition XV The lubricating oil composition was composed of byweight:

Per cent Preparation of Example J 8 57% Ch-containing naphthalene 6Solubilizer 1 Base oil '85 The Timken Procedure No. 1 showed a 12 mg.loss after 16 hours of wear, the surfaces being in good condition. As aresult, the lubricating composition passed this test. The copper stripwas a dark peacock color after 1 hour at 250 F. The Rust Protection Testshowed no rust formation.

I claim:

1. A lubricating oil composition comprising predominantly a mineral oiland containing minor but effective proportions for extreme pressureproperties of an oil-soluble stable chlorinated hydrocarbon containingabout 35 to 75% chlorine and a composition of matter prepared by thereaction of a bicyclic terpene, sulfur, and a phosphorus sulfide in theapproximate molar ratio 38:0.5-5:1, the said composition of mattercontaining sulfur within the range from 10.56 to 16.17 per cent byweight and containing phosphorus within the range from 1.65 to 3.46 percent by weight.

2. A lubricating oil composition comprising predominantly a mineral oiland containing minor but effective proportions for extreme pressureproperties of an oil-soluble stable chlorinated hydrocarbon containingabout 35 to 75% chlorine and sulfurized condensate of alphapinene andphosphorus pentasulfide in which ratio of alpha-pinene to sulfur tophosphorus pentasulfide is approximate 3-8:0.5-5:1, the said sulfiurizedcondensate containing sulfur within the range from 10.56 to 16.17 percent by weight and containing phosphorus within the range from 1.65 to3.46 per cent by weight. I

3. A lubricating oil composition comprising predominantly a mineral oiland containing minor but effective proportions for extreme pressureproperties of an oil-soluble stable chlorinated hydrocarbon containingabout 35 to 75% chlorine and a reaction product of sulfurizedalpha-pinene and phosphorus pentasulfide in which the ratio of alpha-pinene to sulfu'r to phosphorus pentasulfide is approximately3-8:0.5-5:1, the said reaction product containing sulfur within therange from 10.56 to 16.17 per cent by weight and containing phosphoruswithin the range from 1.65 to 3.46 per cent by weight.

4. A lubricating oil composition comprising predominantly a mineral oiland containing minor but effective proportions for extreme pressureproperties of an oil-soluble stable chlorinated hydrocarbon containingabout 35 to 75% chlorine and a composition of matter prepared by thereaction of about 3 to 5 moles of alphapinene, about 0.5 to 5 atoms ofsulfur, and about 1 mole of phosphorus pentasulfide, the saidcomposition of matter containing sulfur within the range from 10.56 to16.17 per cent by weight and containing phosphorus within the range from1.65 to 3.46 per cent by weight.

5. A lubricating oil composition comprising predominantly a mineral oiland containing 3 to 8% of an oil-soluble stable chlorinated hydrocarboncontaining about 35 to 75% chlorine and 4 to 12% of a composition ofmatter prepared by the reaction of alpha-pinene, sulfur, and phosphoruspentasulfide in the approximate molar ratio 3-8:0.5-5:1, the saidcomposition of matter containing sulfur within the range from 10.56 to16.17 per cent by Weight and containing phosphorus within the range from1.65 to 3.46 per cent by weight.

6. A lubricating oil composition comprising predominantly a mineral oiland containing 3 to 8% of an oil-soluble stable chlorinated naphthalenecontaining about 35 to 75% chlorine and 4 to 12% of a composition ofmatter prepared by the reaction of alpha-pinene, sulfur, and

phosphorus pentasulfide in the approximate molar ratio 3-8:0.5-5:1, thesaid composition of matter containing sulfur Within the range from 10.56to 16.17 per cent by Weight and containing phosphorus within the rangefrom 1.65 to 3.46 per cent by weight.

7. A lubricating oil composition comprising predominantly a mineral oiland containing 3 to 8% of an oil-soluble stable chlorinated parafiin Waxcontaining about 35 to 75% chlorine and 4 to 12 of a composition ofmatter prepared by the reaction of alpha-pinene, sulfur, and phosphoruspentasulfide in the approximate molar ratio 3-8:0.5-5:1, the saidcomposition of matter containing sulfur within the range from 10.56 to16.17 per cent by Weight and containing phosphorus Witin the range from1.65 to 3.46 per cent by weight.

8. A lubricating oil composition comprising predominantly a mineral oiland containing about 4 to 6% of an oil-soluble stable chlorin- 14 atedhydrocarbon containing about 35 to 75% chlorine and about 8% of acomposition of mat- -ter prepared by the reaction of alpha-pinene,

sulfur and phosphorus pentasulfide in the approximate ratio of3-8:0.5-5:1, the said composi tion of matter containing sulfur withinthe range from 10.56 to 16.17 per cent by Weight and containingphosphorus Within the range from 1.65 to 3.46 per cent by Weight.

LEONARD E. BEARE.

REFERENCES CITED The following references are of record in the of thispatent:

UNITED STATES PATENTS Sproule et al Apr. 26, 1949

1. A LUBRICATING OIL COMPOSITION COMPRISING PREDOMINANTLY A MINERAL OILAND CONTAINING MINOR BUT EFFECTIVE PROPORTIONS FOR EXTREME PRESSUREPROPERTIES OF AN OIL-SOLUBLE STABLE CHLORINATED HYDROCARBON CONTAININGABOUT 35 TO 75% CHLORINE AND A COMPOSITION OF MATTER PREPARED BY THEREACTION OF BYCYCLIC TERPENE, SULFUR, AND A PHOSPHORUS SULFIDE IN THEAPPROXIMATE MOLAR RATIO 3-8:0''5-5:1, THE SAID COMPOSITION MATTERCONTAINING SULFUR WITHIN THE RANGE FROM 10.56 TO 16.17 PER CENT BYWEIGHT AND CONTAINING PHOSPHORUS WITHIN THE RANGE FROM 1.65 TO 3.46 PERCENT BY WEIGHT.